To reproduce:
Install F13 RC2 from the Xfce live CD
Boot
Take a screenshot with Print Screen, save to ~/Pictures with the default file name (default options)
Run Ristretto from the menus
Do File / Open and attempt to open the screenshot; for me, it's greyed out and unselectable
Note that opening a file manager in ~/Pictures, right-clicking the image, and selecting 'Open with...Ristretto' works fine.

Update - I think I was actually clicking the obvious 'Open' button on the button bar that's invitingly blue when you run the app. This appears to do Open Folder, not Open. So this isn't strictly speaking a bug, though it seems a quite bizarre design. Most apps just conflate Open and Open Folder, for one thing, and Open Folder doesn't seem like it should be the obvious first-choice button?
--
Fedora Bugzappers volunteer triage team
https://fedoraproject.org/wiki/BugZappers

(In reply to comment #1)
> Most apps just conflate Open and Open Folder, for one
> thing, and Open Folder doesn't seem like it should be the obvious first-choice
> button?
Is this a question or a statement? How would you conflate the two commands?
I agree it may not be obvious, especially as 'Open Folder' in the toolbar has the same icon as 'Open' (file) in the menu. However I think that 'Open folder' in the toolbar rather than 'Open' makes sense. Opening single files is usually done by clicking, e.g. in the filemanager while for browsing folders you need to start ristretto first.
Last but not least I think that usability questions should happen upstream in order to reach the developers and a wider audience.

I'm not necessarily suggesting details, that's not my area of expertise. I was simply reporting that, as a dumb end user, the experience on manually running the app for the first time was somewhat confusing to me. I'd suggest we move it upstream and see what their opinion is, and if they feel it's not something it's necessary to address, that's fine.
--
Fedora Bugzappers volunteer triage team
https://fedoraproject.org/wiki/BugZappers

(In reply to comment #5)
> I'm not necessarily suggesting details, that's not my area of expertise. I was
> simply reporting that, as a dumb end user, the experience on manually running
> the app for the first time was somewhat confusing to me.
IMHO for usability questions there is no need for a special expertise, the dumb user you are speaking of is the expert and should also be able to suggest how to do it better.
This is fixed in 0.0.91, the pre-release of the upcoming 1.0. Ristretto now ha two buttons for "Open" and "Open Folder" and the icons in the toolbar and the menu are consistent.

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